Triethanolamine resin



Patented 1938 PATENT OFFICE 2.10am L a 'ramrmomm imam oil-lean Ellis,Montciair, N. 1., assignor'to Ellis- Foster Company, a corporationoiNewler- No Drawing.

Application December 31, 1934, I Serial No. 760,046

22 Claims. (01. zoo-s)- This invention relates to resins formed bycondensing a polybasic acid with a polyhydric compound of thetriethanolamine type. Compounds of the type of triethanolaminecomprehend those substances formed by the reaction of ammonia or aprimary amine withan olefin oxide or its derivatives, such bodies beinghereinafter referred to simply as triethanolamine. a

This is a continuation in part based on my copending application Serial226,826; filed October 17, 1927. a

I have discovered that triethanolamine and phthalic anhydride react onheating to form a resin which polymerizes to an infusibie state'at arelatively lowtemperature. However, a mixture containing 40 partstriethanolamine, 60 parts phthalic anhydride and 3 parts urea can beheated to 240 C. and held at this temperature for 15 minutes .withoutthe formation of any, infusible polymers. Urea acts as a reactionmodifier to prevent formation of infusible substances during the periodof desired reaction necessary to secure a well-reacted productsuitablefor use in varnishes, lacquers and other coating compositions.

The present application deals with resins made from triethanolamine anda poiycarboxylic acid togetherwith drying or non-drying oils and/or theacids obtained from such oils by hydrolysis.

80 An object of this-invention is to provide siccative compositionscomprising a drying oil acid, triethanolamine type of compound and apolybasic acid.

A further object of the invention is to provide compositions, siccativeor non-siccative, which are miscible with rubber in solution or in thedry state, comprising the reaction product of a polybasic acid,amonobasic acid and triethanoL- amine.

In general resihs made from triethanolamine and a polybasic acid' suchas phthalic anhydride, malic acid, maleic anhydride, sebacic acid, orsuccinic acid, are somewhat dark in color unless the temperature is keptlow during the reaction. By'modifying this type of resin, replacing partof the dibasic acid with a monobasic fatty oil acid, 'I have obtainedresins which are hard, but yet retain the original color of the startingmaterials. As described in my parent application 226,326, otherpolybasic acids such as citric, tartaric, fumaric and the like acidsmaybe used in place of, or in addition to the acids named.

Commercial triethanolamine contains the tertiary amine as the principalconstituent, but it also contains some of the secondary amine (diethanolamine) and a small proportion of the primary amine(monoethanolamine). Triethanolamine diii'ers from other polyhydricalcohols in that as well as being an alcohol it is a base. Whentriethanoiamine is mixed with a monobasic fatty acid (or any acid) thefollowing reaction takes place:

In a triethanolamine type compound of the nature here-contemplated, atleast two of the radicals, R, R", R contain hydroxyl groups and theproduct is a polyhydric alcohol which may be further @sinifled with apolybasic acid. For

instance, if RCOOH denotes linoieic acid and RI N13."

denotes triethanoiamine, then the initial com-' pound formed by theabove reaction is triethanolamine linoleate. The difference in this casewhen resiniflcation is effected with, say, phthalic anhydride, is thatthe drying, or fatty oil, acid constituent is directly combined tonitrogen. If three constituents, for instance, phthalic anhydride,linoleic acid and triethanolamine, are heated together, a complexproduct is obtained. Some acid radicals are united with nitrogen; otherswith carbon. Thus, there is an essential difference betweenmodifledpolyhydrlc alcoholpoiybasic acid resins made from non-aminicalcohols and the type comprehended by triethanol amine. 4 v

One object of the invention is to provide resinous compositions madefrom a triethanolamine soap and a polybasic acid.

I have found that resins made according to this invention are misciblein all proportions with rubber in a hydrocarbon solution; such solu-'Besides being other polyhydrid alcohol such as glycerol, glycol,

pentaerythritol, mannitol, etc. Complexes which do not chemicallyresemble the ordinary alkyd resins are thus obtained.

Within this category are included various sensitized oils, that is, oilstreated so as to be capable of incorporation in an unmodified alkydresin. For instance, when a fatty oil is heated with a polyhydricalcohol, redistribution of the fatty oil acid takes place giving amixture of mono-,diand tri-esters which may be resinifled withtriethanolamine and a polybasic acid. Also, when a polybasic acid isheated with, a fatty oil, the oil is partly hydrolyzed to give the freefatty acid and a part-ester of the glycerideoil and the polybasic acid.-Such a sensitized oil may be further reacted with triethanolamine togive a resinous product. Also, fattyoils can be sensitized by heatingwith triethanolamine. In this case sev'eral reactions mayoccur, such asformation of an amine soap, or an ester of the alkylolamine and thefatty acids which split oil, or formation of mixed soap-esters. Any ofthese or their mixtures may then be further resinified by heating with apolybasic acid.

In general the resins from a polybasic acid, a monobasic acid andtriethanolamine are soluble in drying oils. In this way they may becompounded into varnishes and used as coating compositions.

When triethanolamine is heated with a dryin oil acid, a compound isformed which in itself may be used as a varnish base. When dissolved insuitable solvents such as V. M. 8: P. naphtha, solvent naphtha, orturpentine and about 2.5 per cent lead-cobalt drier solution added, afast-dry- "readily compatible with rubber, both in hydrocarbon solutionand in a dry film.

The following are several examples given to further illustrate themethods of preparing the resins described he'reinabove:

Example 1 Parts by weight Commercial triethanolamine 20 Phtbalicanhydride -s 25 linseed oil fatty acids 10 "The reaction mixture isallowedto increase in viscosity until almost a gel and is then rapidlycooled to room temperature. The product is. light-colored, sticky andhas slightly rubbery, characteristics. It is readily soluble in toluol.j A varnish may be made from s11ch a-composi-.- tion as above describedby dissolving it in toluol, or a mixture of toluol and V. M. a P.naphtha,'to the desired consistency, then adding lead-cobalt driers. I

minutes at 200 C., the resin becomes clear and readily into thephthalic-amine complex. Con- Example 2- I 1 Y Parts Triethanolamine";20' Phthalic anhydride 25 Tung oil fatty acids 10 5 about 170- C. Thetung oil fatty acids react very readily into the phthalic-amine'iresin.In about 2 10 remains clear on cooling a test sample to roomtemperature. The mixture is light in color and does not darkenappreciably during the heating. The resin has a tendency to gel rapidly.It thickens in about 10 minutes of heating at 200 C. to an almostinfusible stage. However, before this change set in, the mixture may becooled rapidly to room temperature, in which case the final material islight-colored, brittle yet sticky, and slightly rubbery. 'It' is readilysoluble in toluol and miscible with rubber.

A varnish film from this resin containing driers dries in about 4 hours.

Example 3 $5 Parts.' Commercial triethanolamine 20 Phthalic anhydride 20Linseed oil fatty acids 40 m These materials are heated together to200-210 C. for about 10- minutes, then at 230 C.-for hour, during whichtime the mixture increases in viscosity. At this stage the mixture isclear on cooling to room temperature. Heating is con-. tinued for about15 minutes longer at 230 C., but during this further. heating does notincrease noticeably in viscosity. At room temperature the material is alight-colored, soft, sticky resin. It

is readily soluble in toluol and in a mixture of toluol and mineralspirits.

Example 4 Parts Triethanolamine ,20 Phthalic anhydride 20 45 Tung oilfatty acids 40 These constituents are heated together at 210 C. forabout 5 minutes, then at 230 C. for 10 minutes. The tung oil fatty acidscombine very tinued heating at 230 C. shows a tendency for the mixtureto gel. The product is, therefore, cooled to room temperature beforegelling occurs. It is a very soft, sticky solid, light in color andreadily soluble in toluol and a toluol-mineral spirits mixture.

Varnishes made from this material dry dustfree in from 1% to 2 hours andare hard in from 3% to 4%, hours.

00 Example 5 Product from Example 4 2 Raw tung oil 1 These materials aremixed and heated to 240 C. 65

These two constituents are heated to 210' C. for about 15 minutes, thento 250 C. forabout hour. At the end of this time the product no longersolidifies, but remains liquid. It has a consistency of a very viscousoil at room temperature.

10 g. of the above product are dissolved in 12 g. of V. M. & P. naphthaand 0.25 g. of a 33.3% solu tion of lead-cobalt naphthenate driersolution in V. M. & P. naphtha is added. A film of this varnish driesdust-free in 1 hours and is dry in 3 to 4 hours.

If the above product is dissolved in toluol it may be mixed with atoluol solution of gum rubber in any proportion. Such solutions dry togive perfectly clear films.

Example 7 Parts Commercial triethanolamine; 15 Phthalic anhydride 15 Rawtung oil 15 Rosin (W. W.) 30

such that at room-temperature it is a somewhat.

soft, but brittle solid, heating is stopped.

The final product is readily soluble in toluol, benzol, xylol, a mixtureof these solvents with alcohol and a mixture of these solvents with V.M. 8; P. naphtha.

When about 1 per cent drier based on the resin is added a quick-dryingvarnish is produced. A film when dry is practically water-white.

Example 8' I Part by weight Resin of Example 7 1 Raw tung oil 1 Theseare heated to 240 C. for minutes. The resin is very readily soluble inthe tung oil and dissolves immediately as the resin becomes molten.Another method is to dissolve thetwo constituents in a solvent and, mixthe solutions.

When made into a varnish containing about 3 per cent leadcobaltnaphthenate drier solution based on the resin, a film dries dust-free inabout 1 hour and is entirely dry in 3 to 4 hours.

Included under the term triethanolamine type are various other amines ofmore or less corresponding nature; such as those of propyl alcohol andother alcohol derivatives.

As pointed out in my application Serial No. 226,826, my invention isconcernedlwith products derived from an organic acid or a plurality ofsuch acids. These acids include such polybasic acids as succinic.citric, malic, maleic, fumaric, phthalic, tartaric, adipic, azelaic,suberic; etc. Also such fatty acids as those derived from the animal andvegetable oils including. lauric, myristic, palmitic,steari c, oleic,linoleic, linolenic, etc.

What Iclaim is:

1. A resin comprising the reaction product of phthalic anhydride,triethanolamine and a drying oil fatty acid.

2. A synthetic resin including the reaction product of triethanolaminewith an organic carboxylic acid.

3. A synthetic resin consisting of the reaction product oftriethanolamine with-an organic carboxylic acid.

4. A synthetic resin including the reaction product of triethanolaminewith phthalic an hydride.

5. A synthetic resin including the reaction product of triethanolaminewith phthalic anhydride, and an aliphatic carboxylic acid.

6. A synthetic resin including the reaction product of triethanolaminewith a polybasic organic carboxylic acid.

7. A synthetic resin consisting of the reaction products of polyhydricalcohols including triethanolamine with an organic carboxylic acid.

8. A synthetic resin consisting of the reaction products of po yhydricalcohols including triethanolamine with'a polybasic organic carboxylicacid.

9. A synthetic resin consisting of the reaction products of polyhydricalcohols -including triethanolamine with, phthalic anhydride.

10. A synthetic resin consisting of the reaction products of polyhydricalcohols including triethanolamine with phthalic anhydride and analiphatic carboxylic acid. 1

11. A synthetic resin consisting of the reaction product oftriethanolamine with a polybasic organic carboxylic acid. 1

12. The method of producing synthetic resins which comprises heating amixture of triethanolamine with' a polybasic organic carboxylic acid.

13. The method of producing synthetic resins which comprises heating amixture of methanol-- amine with phthalic anhydride.

14. The method of producing synthetic resins which comprises heating amixture of t1iethanolamine with phthalic anhydride and an aliphaticcarboxylic acid.

15. The method of producing synthetic resins which comprises heating amixture of triethanolamine with a mixture of organic carboxylic acidsincluding a polybasic acid. I

16. A synthetic resin including the reaction products of triethanolaminewith phthalic anhydride and an organic carboxylic acid. 17. A syntheticresin consisting of the reaction products of polyhydric alcoholsincluding triethanolamine with phthalic anhydride and an organiccarboxylic acid. Y

18. A synthetic resin consisting of the reaction products oftriethanolamine with phthalic anhydride and an organic carboxylic acid.

19. The method of producing synthetic resins which comprises heating amixture of triethanolamine with an organic carboxylic acid.

20. The method'of producing Synthetic resins which comprises heating amixture of polyhy- 22. The method of producing synthetic resins whichcomprises heating a mixture of triethanolamine and one or more-of theacids of the group consisting oi phthalic anhydride, oleic, citric,tartaric, maleic, maiic and fumaric acids.

. CARLETON ELLIS.

